In this study, porous carbon aerogel (CA) was synthesized with D-glucose, ammonium persulfate and aniline by a hydrothermal carbonization method. It was reported for the first time as an excellent catalyst for activating persulfate (PS) to degrade rhodamine B (RhB). The morphology of CA was characterized, exhibiting microporous and mesoporous structures. The solution pH of 3, 5, 7 and 9 showed slight impact on the degradation of RhB; however, when the pH increased to 11, the removal of RhB decreased. The PS concentration and CA dosage played a key role in the RhB degradation, and the activation energy was calculated to be 22.11 kJ/mol. Electron paramagnetic resonance (EPR) spectra suggested that neither sulfate radical (SO4 center dot(-)) nor hydroxyl radical (center dot OH) was generated from the PS activation. The radical quenching experiments also confirmed that CA activated PS in a non-radical pathway. It was indicated that PS bonded with C=C in the sp(2) hybridized system could directly degrade RhB. The defective edges at the boundary of CA also facilitated the RhB removal. This work presented a green material with both excellent catalytic performance and high regeneration possibility in the heterogeneous metal-free PS activation, providing a new strategy in water treatment.